EP3593367A1 - Ensemble condensateur à électrolyte solide - Google Patents

Ensemble condensateur à électrolyte solide

Info

Publication number
EP3593367A1
EP3593367A1 EP18763444.9A EP18763444A EP3593367A1 EP 3593367 A1 EP3593367 A1 EP 3593367A1 EP 18763444 A EP18763444 A EP 18763444A EP 3593367 A1 EP3593367 A1 EP 3593367A1
Authority
EP
European Patent Office
Prior art keywords
capacitor assembly
anode
coating
termination
capacitor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18763444.9A
Other languages
German (de)
English (en)
Other versions
EP3593367A4 (fr
Inventor
Mitchell D. Weaver
Jan Petrzilek
Miloslav Uher
Frantisek Priban
Tomas Hofirek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Avx Components Corp
Original Assignee
AVX Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AVX Corp filed Critical AVX Corp
Publication of EP3593367A1 publication Critical patent/EP3593367A1/fr
Publication of EP3593367A4 publication Critical patent/EP3593367A4/fr
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/008—Terminals
    • H01G9/012—Terminals specially adapted for solid capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H01G9/0525—Powder therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/08—Housing; Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes

Definitions

  • Electrolytic capacitors e.g., tantalum capacitors
  • electrolytic capacitors are increasingly being used in the design of circuits due to their volumetric efficiency, reliability, and process compatibility.
  • a solid electrolytic capacitor element that includes a tantalum anode, dielectric layer, and conductive polymer solid electrolyte.
  • the anode is connected to an anode termination and the solid electrolyte is connected to a cathode termination.
  • the capacitor element is also encapsulated with a resinous casing material (e.g., epoxy resin) so that a portion of the anode and cathode terminations remain exposed for mounting to a surface.
  • micro-cracks can form in the anode and/or cathode terminations. When exposed to high humidity levels, these micro-cracks can absorb moisture, which can result in oxidation of the conductive polymer solid electrolyte and lead to a rapid deterioration of the electrical properties.
  • a capacitor assembly comprising a solid electrolytic capacitor element that contains a sintered porous anode body, a dielectric that overlies the anode body, and a solid electrolyte that overlies the dielectric.
  • An anode termination is in electrical connection with the anode body and a cathode termination is in electrical connection with the solid electrolyte.
  • a first coating is disposed on at least a portion of the anode termination that contains an organometallic compound and a second coating is disposed on at least a portion of the cathode termination that contains an organometallic compound.
  • a casing material encapsulates the capacitor element and leaves exposed a mounting surface of the anode termination and the cathode termination.
  • Fig. 1 is a schematic illustration of one embodiment of a capacitor that may be formed in accordance with the present invention.
  • the present invention is directed to a capacitor assembly that contains a capacitor element that contains a sintered porous anode body, a dielectric overlying the anode body, and a solid electrolyte overlying the dielectric.
  • the anode body is in electrical contact with an anode termination and the solid electrolyte is in electrical contact with a cathode termination.
  • the capacitor element is encapsulated with a casing material so that at least one surface of the anode termination and the cathode termination remains exposed for mounting to an electronic component (e.g., printed circuit board).
  • a first coating is disposed on at least a portion of the anode termination and a second coating is disposed on at least a portion of the cathode termination.
  • the first and second coatings contain an organometallic compound, which can improve the adhesion of the casing material to the terminations and thus help to reduce the number of micro-cracks that would otherwise form after exposure to high temperatures (e.g., during reflow), such as at a peak reflow temperature of from about 150°C to about 350°C, and in some embodiments, from 200°C to about 300°C (e.g., 250°C).
  • the resulting capacitor assembly is not highly sensitive to moisture and can thus exhibit excellent electrical properties even when exposed to high humidity levels, such as when placed into contact with an atmosphere having a relative humidity of about 40% or more, in some
  • Relative humidity may, for instance, be determined in accordance with ASTM E337-02, Method A (2007).
  • the humid atmosphere may be part of the internal atmosphere of the capacitor assembly itself, or it may be an external atmosphere to which the capacitor assembly is exposed during storage and/or use.
  • the capacitor may, for instance, exhibit a relatively low equivalence series resistance ("ESR") when exposed to the high humidity atmosphere (e.g., 60% relative humidity), such as about 200 mohms, in some embodiments less than about 150 mohms, in some embodiments from about 0.01 to about 125 mohms, and in some embodiments, from about 0.1 to about 100 mohms, measured at an operating frequency of 100 kHz.
  • ESR equivalence series resistance
  • the capacitor assembly may exhibit a DCL of only about 50 microamps (" ⁇ ") or less, in some embodiments about 40 ⁇ or less, in some embodiments about 20 ⁇ or less, and in some embodiments, from about 0.1 to about 10 ⁇ .
  • the capacitor assembly may also exhibit a high percentage of its wet capacitance, which enables it to have only a small capacitance loss and/or fluctuation in the presence of atmosphere humidity. This performance
  • the capacitor assembly may exhibit a wet-to-dry capacitance percentage of about 50% or more, in some embodiments about 60% or more, in some
  • the dry capacitance may be about 30 nanoFarads per square centimeter ("nF/cm 2 ") or more, in some embodiments about 100 nF/cm 2 or more, in some embodiments from about 200 to about 3,000 nF/cm 2 , and in some embodiments, from about 400 to about 2,000 nF/cm 2 , measured at a frequency of 120 Hz.
  • nF/cm 2 nanoFarads per square centimeter
  • the ESR, DCL, and capacitance values may even be maintained for a substantial amount of time at the high humidity levels.
  • the values may be maintained for about 10 hours or more, in some embodiments from about 20 hours to about 30 hours, and in some embodiments, from about 40 hours to about 80 hours (e.g., 24 hours, 48 hours, or 72 hours) when tested at a temperature of from about 20°C to about 50°C, and in some embodiments, from 25°C to about 40°C (e.g., 30°C).
  • the capacitor element includes an anode that contains a dielectric formed on a sintered porous body.
  • the porous anode body may be formed from a powder that contains a valve metal (i.e., metal that is capable of oxidation) or valve metal- based compound, such as tantalum, niobium, aluminum, hafnium, titanium, alloys thereof, oxides thereof, nitrides thereof, and so forth.
  • the powder is typically formed from a reduction process in which a tantalum salt (e.g., potassium fluotantalate (K 2 TaF 7 ), sodium fluotantalate (Na 2 TaF 7 ), tantalum pentachloride (TaCIs), etc.) is reacted with a reducing agent.
  • a tantalum salt e.g., potassium fluotantalate (K 2 TaF 7 ), sodium fluotantalate (Na 2 TaF 7 ), tantalum pentachloride (TaCIs), etc.
  • the reducing agent may be provided in the form of a liquid, gas (e.g., hydrogen), or solid, such as a metal (e.g., sodium), metal alloy, or metal salt.
  • a tantalum salt e.g., TaCIs
  • TaCIs may be heated at a temperature of from about 900°C to about 2,000°C, in some embodiments from about 1 ,000°C to about 1 ,800°C, and in some embodiments, from about 1 , 100°C to about 1 ,600°C, to form a vapor that can be reduced in the presence of a gaseous reducing agent (e.g., hydrogen). Additional details of such a reduction reaction may be described in WO
  • the product may be cooled, crushed, and washed to form a powder.
  • the specific charge of the powder typically varies from about 2,000 to about 800,000 microFarads * Volts per gram (" F * V/g") depending on the desired application
  • a high charge powder may be employed that has a specific charge of from about 100,000 to about 800,000 F*V/g, in some embodiments from about 120,000 to about 700,000 ⁇ F* ⁇ //g, and in some embodiments, from about 150,000 to about 600,000
  • a low charge powder may be employed that has a specific charge of from about 2,000 to about 100,000 MF*V/g, in some embodiments from about 5,000 to about 80,000 ⁇ /Zg, and in some embodiments, from about 10,000 to about 70,000 ⁇ F* ⁇ //g.
  • the specific charge may be
  • the powder may be a free-flowing, finely divided powder that contains primary particles.
  • the primary particles of the powder generally have a median size (D50) of from about 5 to about 500 nanometers, in some embodiments from about 10 to about 400 nanometers, and in some embodiments, from about 20 to about 250 nanometers, such as determined using a laser particle size distribution analyzer made by BECKMAN COULTER Corporation (e.g. , LS-230), optionally after subjecting the particles to an ultrasonic wave vibration of 70 seconds.
  • the primary particles typically have a three-dimensional granular shape (e.g. , nodular or angular). Such particles typically have a relatively low "aspect ratio", which is the average diameter or width of the particles divided by the average thickness ("D/T").
  • the aspect ratio of the particles may be about 4 or less, in some embodiments about 3 or less, and in some embodiments, from about 1 to about 2.
  • the powder may also contain other types of particles, such as secondary particles formed by aggregating (or agglomerating) the primary particles.
  • secondary particles may have a median size (D50) of from about 1 to about 500 micrometers, and in some embodiments, from about 10 to about 250 micrometers.
  • Agglomeration of the particles may occur by heating the particles and/or through the use of a binder. For example, agglomeration may occur at a
  • Suitable binders may likewise include, for instance, polyvinyl butyral); polyvinyl acetate); polyvinyl alcohol); polyvinyl pyrollidone); cellulosic polymers, such as carboxymethylcellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and methylhydroxyethyl cellulose; atactic polypropylene, polyethylene;
  • polyethylene glycol e.g., Carbowax from Dow Chemical Co.
  • polystyrene poly(butadiene/styrene); polyamides, polyimides, and polyacrylamides, high molecular weight polyethers
  • copolymers of ethylene oxide and propylene oxide fluoropolymers, such as polytetrafluoroethylene, polyvinylidene fluoride, and fluoro- olefin copolymers
  • acrylic polymers such as sodium polyacrylate, poly(lower alkyi acrylates), poly(lower alkyi methacrylates) and copolymers of lower alkyi acrylates and methacrylates
  • fatty acids and waxes such as stearic and other soapy fatty acids, vegetable wax, microwaxes (purified paraffins), etc.
  • the resulting powder may be compacted to form a pellet using any conventional powder press device.
  • a press mold may be employed that is a single station compaction press containing a die and one or multiple punches.
  • anvil-type compaction press molds may be used that use only a die and single lower punch.
  • Single station compaction press molds are available in several basic types, such as cam, toggle/knuckle and eccentric/crank presses with varying capabilities, such as single action, double action, floating die, movable platen, opposed ram, screw, impact, hot pressing, coining or sizing.
  • the powder may be compacted around an anode lead, which may be in the form of a wire, sheet, etc.
  • the lead may extend in a longitudinal direction from the anode body and may be formed from any electrically conductive material, such as tantalum, niobium, aluminum, hafnium, titanium, etc., as well as electrically conductive oxides and/or nitrides of thereof. Connection of the lead may also be accomplished using other known techniques, such as by welding the lead to the body or embedding it within the anode body during formation (e.g., prior to compaction and/or sintering).
  • any binder may be removed after pressing by heating the pellet under vacuum at a certain temperature (e.g., from about 150°C to about 500°C) for several minutes.
  • the binder may also be removed by contacting the pellet with an aqueous solution, such as described in U.S. Patent No. 6, 197,252 to Bishop, et al.
  • the pellet is sintered to form a porous, integral mass.
  • the pellet is typically sintered at a temperature of from about 700°C to about 1600°C, in some embodiments from about 800°C to about 1500°C, and in some embodiments, from about 900°C to about 1200°C, for a time of from about 5 minutes to about 100 minutes, and in some embodiments, from about 8 minutes to about 15 minutes.
  • sintering may occur in an atmosphere that limits the transfer of oxygen atoms to the anode.
  • sintering may occur in a reducing atmosphere, such as in a vacuum, inert gas, hydrogen, etc.
  • the reducing atmosphere may be at a pressure of from about 10 Torr to about 2000 Torr, in some embodiments from about 100 Torr to about 1000 Torr, and in some embodiments, from about 100 Torr to about 930 Torr.
  • Mixtures of hydrogen and other gases e.g., argon or nitrogen may also be employed.
  • the anode is also coated with a dielectric.
  • the dielectric may be formed by anodically oxidizing (“anodizing”) the sintered anode so that a dielectric layer is formed over and/or within the anode.
  • anodizing anodically oxidizing
  • a tantalum (Ta) anode may be anodized to tantalum pentoxide (Ta 2 0 5 ).
  • anodization is performed by initially applying a solution to the anode, such as by dipping anode into the electrolyte.
  • a solvent is generally employed, such as water (e.g., deionized water).
  • a compound may be employed that is capable of dissociating in the solvent to form ions.
  • an acid e.g., phosphoric acid
  • an acid may constitute from about 0.01 wt.% to about 5 wt.%, in some embodiments from about 0.05 wt.% to about 0.8 wt.%, and in some embodiments, from about 0.1 wt.% to about 0.5 wt.% of the anodizing solution.
  • blends of acids may also be employed.
  • a current is passed through the anodizing solution to form the dielectric layer.
  • the value of the formation voltage manages the thickness of the dielectric layer.
  • the power supply may be initially set up at a galvanostatic mode until the required voltage is reached. Thereafter, the power supply may be switched to a potentiostatic mode to ensure that the desired dielectric thickness is formed over the entire surface of the anode.
  • a potentiostatic mode to ensure that the desired dielectric thickness is formed over the entire surface of the anode.
  • other known methods may also be employed, such as pulse or step potentiostatic methods.
  • the voltage at which anodic oxidation occurs typically ranges from about 4 to about 250 V, and in some embodiments, from about 5 to about 200 V, and in some embodiments, from about 10 to about 150 V.
  • the anodizing solution can be kept at an elevated temperature, such as about 30°C or more, in some embodiments from about 40°C to about 200°C, and in some embodiments, from about 50°C to about 100°C.
  • Anodic oxidation can also be done at ambient temperature or lower.
  • the resulting dielectric layer may be formed on a surface of the anode and within its pores.
  • the dielectric layer may possess a differential thickness throughout the anode in that it possesses a first portion that overlies an external surface of the anode and a second portion that overlies an interior surface of the anode.
  • the first portion is selectively formed so that its thickness is greater than that of the second portion.
  • the thickness of the dielectric layer need not be uniform within a particular region. Certain portions of the dielectric layer adjacent to the external surface may, for example, actually be thinner than certain portions of the layer at the interior surface, and vice versa. Nevertheless, the dielectric layer may be formed such that at least a portion of the layer at the external surface has a greater thickness than at least a portion at the interior surface.
  • the ratio of the thickness of the first portion to the thickness of the second portion is typically from about 1 .2 to about 40, in some embodiments from about 1 .5 to about 25, and in some embodiments, from about 2 to about 20.
  • a multi-stage process is generally employed.
  • the sintered anode is anodically oxidized ("anodized") to form a dielectric layer (e.g., tantalum
  • a relatively small forming voltage is typically employed to ensure that the desired dielectric thickness is achieved for the inner region, such as forming voltages ranging from about 1 to about 90 volts, in some embodiments from about 2 to about 50 volts, and in some embodiments, from about 5 to about 20 volts.
  • the sintered body may then be anodically oxidized in a second stage of the process to increase the thickness of the dielectric to the desired level.
  • anodizing in an electrolyte at a higher voltage than employed during the first stage such as at forming voltages ranging from about 50 to about 350 volts, in some embodiments from about 60 to about 300 volts, and in some embodiments, from about 70 to about 200 volts.
  • the electrolyte may be kept at a temperature within the range of from about 15°C to about 95°C, in some embodiments from about 20°C to about 90°C, and in some embodiments, from about 25°C to about 85°C.
  • the electrolytes employed during the first and second stages of the anodization process may be the same or different. Typically, however, it is desired to employ different solutions to help better facilitate the attainment of a higher thickness at the outer portions of the dielectric layer.
  • the electrolyte employed in the second stage has a lower ionic conductivity than the electrolyte employed in the first stage to prevent a significant amount of oxide film from forming on the internal surface of anode.
  • the electrolyte employed during the first stage may contain an acidic compound, such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid, boronic acid, etc.
  • Such an electrolyte may have an electrical conductivity of from about 0.1 to about 100 mS/cm, in some embodiments from about 0.2 to about 20 mS/cm, and in some embodiments, from about 1 to about 10 mS/cm, determined at a temperature of 25°C.
  • the electrolyte employed during the second stage typically contains a salt of a weak acid so that the hydronium ion concentration increases in the pores as a result of charge passage therein. Ion transport or diffusion is such that the weak acid anion moves into the pores as necessary to balance the electrical charges.
  • the concentration of the principal conducting species is reduced in the establishment of equilibrium between the hydronium ion, acid anion, and undissociated acid, thus forms a poorer-conducting species.
  • the reduction in the concentration of the conducting species results in a relatively high voltage drop in the electrolyte, which hinders further anodization in the interior while a thicker oxide layer, is being built up on the outside to a higher formation voltage in the region of continued high conductivity.
  • Suitable weak acid salts may include, for instance, ammonium or alkali metal salts (e.g., sodium, potassium, etc.) of boric acid, boronic acid, acetic acid, oxalic acid, lactic acid, adipic acid, etc.
  • Particularly suitable salts include sodium tetraborate and ammonium pentaborate.
  • Such electrolytes typically have an electrical conductivity of from about 0.1 to about 20 mS/cm, in some embodiments from about 0.5 to about 10 mS/cm, and in some embodiments, from about 1 to about 5 mS/cm, determined at a temperature of 25°C.
  • each stage of anodization may be repeated for one or more cycles to achieve the desired dielectric thickness.
  • the anode may also be rinsed or washed with another solvent (e.g., water) after the first and/or second stages to remove the electrolyte.
  • another solvent e.g., water
  • a solid electrolyte overlies the dielectric and generally functions as the cathode for the capacitor assembly.
  • the solid electrolyte may include materials as is known in the art, such as conductive polymers (e.g., polypyrroles, polythiophenes, polyanilines, etc.), manganese dioxide, and so forth.
  • the solid electrolyte contains one or more layers containing extrinsically and/or intrinsically conductive polymer particles.
  • ionic species e.g., Fe 2+ or Fe 3+
  • the resulting capacitor may exhibit a relatively high "breakdown voltage.”
  • the solid electrolyte may be formed from one or multiple layers. When multiple layers are employed, it is possible that one or more of the layers includes a conductive polymer formed by in situ polymerization. However, when it is desired to achieve very high breakdown voltages, the present inventors have discovered that the solid electrolyte is formed primarily from the conductive particles described above, and that it is generally free of conductive polymers formed via in situ polymerization.
  • the resulting solid electrolyte typically has a total a thickness of from about 1 micrometer (pm) to about 200 pm, in some embodiments from about 2 pm to about 50 pm, and in some embodiments, from about 5 pm to about 30 pm.
  • Thiophene polymers are particularly suitable for use in the solid
  • an "extrinsically" conductive thiophene polymer may be employed in the solid electrolyte that has repeating units of the following formula (III):
  • R 7 is a linear or branched, Ci to d 8 alkyl radical (e.g., methyl, ethyl, n- or iso-propyl, n- iso-, sec- or tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1 -ethylpropyl, 1 , 1 -dimethylpropyl, 1 ,2-dimethylpropyl, 2,2- dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.); C 5 to
  • q is an integer from 0 to 8, in some embodiments, from 0 to 2, and in one embodiment, 0.
  • "q" is 0 and the polymer is poly(3,4- ethylenedioxythiophene).
  • a monomer suitable for forming such a polymer is 3,4-ethylenedioxthiophene, which is available from Heraeus under the designation CleviosTM M.
  • the polymers of formula (III) are generally considered to be "extrinsically" conductive to the extent that they typically require the presence of a separate counterion that is not covalently bound to the polymer.
  • the counterion may be a monomeric or polymeric anion that counteracts the charge of the conductive polymer.
  • Polymeric anions can, for example, be anions of polymeric carboxylic acids (e.g., polyacrylic acids, polymethacrylic acid, polymaleic acids, etc.);
  • polymeric sulfonic acids e.g., polystyrene sulfonic acids ("PSS"), polyvinyl sulfonic acids, etc.
  • PSS polystyrene sulfonic acids
  • the acids may also be copolymers, such as copolymers of vinyl carboxylic and vinyl sulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
  • suitable monomeric anions include, for example, anions of Ci to C 2 o alkane sulfonic acids (e.g., dodecane sulfonic acid); aliphatic perfluorosulfonic acids (e.g., trifluoromethane sulfonic acid, perfluorobutane sulfonic acid or perfluorooctane sulfonic acid); aliphatic Ci to C 20 carboxylic acids (e.g., 2-ethyl-hexylcarboxylic acid); aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acid or perfluorooctanoic acid); aromatic sulfonic acids optionally substituted by Ci to C 20 alkyl groups (e.g., benzene sulfonic acid, o- toluene sulfonic acid, p-toluene sulfonic acid or dodecylbenz
  • Particularly suitable counteranions are polymeric anions, such as a polymeric carboxylic or sulfonic acid (e.g., polystyrene sulfonic acid (“PSS”)).
  • PSS polystyrene sulfonic acid
  • the molecular weight of such polymeric anions typically ranges from about 1 ,000 to about 2,000,000, and in some embodiments, from about 2,000 to about 500,000.
  • Intrinsically conductive polymers may also be employed that have a positive charge located on the main chain that is at least partially compensated by anions covalently bound to the polymer.
  • a suitable intrinsically conductive thiophene polymer may have repeating units of the following formula (IV):
  • a is from 0 to 10, in some embodiments from 0 to 6, and in some
  • b is from 1 to 18, in some embodiments from 1 to 10, and in some embodiments, from 2 to 6 (e.g., 2, 3, 4, or 5);
  • Z is an anion, such as S0 3 “ , C(0)0 “ , BF 4 “ , CF3SO3 “ , SbF 6 “ , N(S0 2 CF 3 ) 2 “ ,
  • X is a cation, such as hydrogen, an alkali metal (e.g., lithium, sodium, rubidium, cesium or potassium), ammonium, etc.
  • Z in formula (IV) is a sulfonate ion such that the intrinsically conductive polymer contains repeating units of the following formula (V):
  • R and X are defined above.
  • a is preferably 1 and b is preferably 3 or 4.
  • X is preferably sodium or potassium.
  • the polymer may be a copolymer that contains other types of repeating units.
  • the repeating units of formula (IV) typically constitute about 50 mol.% or more, in some embodiments from about 75 mol.% to about 99 mol.%, and in some embodiments, from about 85 mol.% to about 95 mol.% of the total amount of repeating units in the copolymer.
  • the polymer may also be a homopolymer to the extent that it contains 100 mol.% of the repeating units of formula (IV).
  • homopolymers include poly(4-(2,3-dihydrothieno-[3,4-b][1 ,4]dioxin-2-ylmethoxy)-1 - butane-sulphonic acid, salt) and poly(4-(2,3-dihydrothieno-[3,4-b][l,4]dioxin-2- ylmethoxy)-l-propanesulphonic acid, salt).
  • the resulting conductive polymer particles typically have an average size (e.g., diameter) of from about 1 to about 80 nanometers, in some embodiments from about 2 to about 70
  • the diameter of the particles may be determined using known techniques, such as by ultracentrifuge, laser diffraction, etc.
  • the shape of the particles may likewise vary. In one particular embodiment, for instance, the particles are spherical in shape. However, it should be understood that other shapes are also contemplated by the present invention, such as plates, rods, discs, bars, tubes, irregular shapes, etc.
  • the conductive polymer particles may be applied in the form of a dispersion.
  • concentration of the conductive polymer in the dispersion may vary depending on the desired viscosity of the dispersion and the particular manner in which the dispersion is to be applied to the capacitor element.
  • the polymer constitutes from about 0.1 to about 10 wt.%, in some embodiments from about 0.4 to about 5 wt.%, and in some embodiments, from about 0.5 to about 4 wt.% of the dispersion.
  • the dispersion may also contain one or more components to enhance the overall properties of the resulting solid electrolyte.
  • the dispersion may contain a binder to further enhance the adhesive nature of the polymeric layer and also increase the stability of the particles within the dispersion.
  • the binder may be organic in nature, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyvinyl chlorides, polyvinyl acetates, polyvinyl butyrates, polyacrylic acid esters, polyacrylic acid amides, polymethacrylic acid esters, polymethacrylic acid amides, polyacrylonitriles, styrene/acrylic acid ester, vinyl acetate/acrylic acid ester and ethylene/vinyl acetate copolymers, polybutadienes, polyisoprenes, polystyrenes, polyethers, polyesters, polycarbonates, polyurethanes, polyamides, polyimides, polysulfones, melamine formaldehyde resins, epoxide resins, silicone resins or celluloses.
  • Dispersion agents may also be employed to facilitate the ability to apply the layer to the anode.
  • Suitable dispersion agents include solvents, such as aliphatic alcohols (e.g., methanol, ethanol, i-propanol and butanol), aliphatic ketones (e.g., acetone and methyl ethyl ketones), aliphatic carboxylic acid esters (e.g., ethyl acetate and butyl acetate), aromatic hydrocarbons (e.g., toluene and xylene), aliphatic hydrocarbons (e.g., hexane, heptane and cyclohexane), chlorinated hydrocarbons (e.g.,
  • dichloromethane and dichloroethane aliphatic nitriles (e.g., acetonitrile), aliphatic sulfoxides and sulfones (e.g., dimethyl sulfoxide and sulfolane), aliphatic carboxylic acid amides (e.g., methylacetamide, dimethylacetamide and dimethylformamide), aliphatic and araliphatic ethers (e.g., diethylether and anisole), water, and mixtures of any of the foregoing solvents.
  • a particularly suitable dispersion agent is water.
  • fillers may be used that have a size of from about 10 nanometers to about 100 micrometers, in some embodiments from about 50 nanometers to about 50 micrometers, and in some embodiments, from about 100 nanometers to about 30 micrometers.
  • fillers include calcium carbonate, silicates, silica, calcium or barium sulfate, aluminum hydroxide, glass fibers or bulbs, wood flour, cellulose powder carbon black, electrically conductive polymers, etc.
  • the fillers may be introduced into the dispersion in powder form, but may also be present in another form, such as fibers.
  • Surface-active substances may also be employed in the dispersion, such as ionic or non-ionic surfactants.
  • adhesives may be employed, such as organofunctional silanes or their hydrolysates, for example 3- glycidoxypropyltrialkoxysilane, 3-aminopropyl-triethoxysilane, 3-mercaptopropyl- trimethoxysilane, 3-metacryloxypropyltrimethoxysilane, vinyltrimethoxysilane or octyltriethoxysilane.
  • the dispersion may also contain additives that increase conductivity, such as ether group-containing compounds (e.g., tetrahydrofuran), lactone group-containing compounds (e.g., ⁇ -butyrolactone or ⁇ -valerolactone), amide or lactam group-containing compounds (e.g., caprolactam, N- methylcaprolactam, ⁇ , ⁇ -dimethylacetamide, N-methylacetamide, N,N- dimethylformamide (DMF), N-methylformamide, N-methylformanilide, N- methylpyrrolidone (NMP), N-octylpyrrolidone, or pyrrolidone), sulfones and sulfoxides (e.g., sulfolane (tetramethylenesulfone) or dimethylsulfoxide (DMSO)), sugar or sugar derivatives (e.g., saccharose, glucose, fructose, or lactose), sugar alcohols
  • the dispersion may be applied using a variety of known techniques, such as by spin coating, impregnation, pouring, dropwise application, injection, spraying, doctor blading, brushing, printing (e.g., ink-jet, screen, or pad printing), or dipping.
  • the viscosity of the dispersion is typically from about 0.1 to about 100,000 mPas (measured at a shear rate of 100 s "1 ), in some embodiments from about 1 to about 10,000 mPas, in some embodiments from about 10 to about 1 ,500 mPas, and in some embodiments, from about 100 to about 1000 mPas.
  • the solid electrolyte is generally formed from one or more "inner" conductive polymer layers.
  • the term “inner” in this context refers to one or more layers that overly the dielectric, whether directly or via another layer (e.g., pre- coat layer).
  • One or multiple inner layers may be employed.
  • the solid electrolyte typically contains from 2 to 30, in some embodiments from 4 to 20, and in some embodiments, from about 5 to 15 inner layers (e.g. , 10 layers).
  • the inner layer(s) may, for example, contain intrinsically and/or extrinsically conductive polymer particles such as described above.
  • such particles may constitute about 50 wt.% or more, in some embodiments about 70 wt.% or more, and in some embodiments, about 90 wt.% or more (e.g., 100 wt.%) of the inner layer(s).
  • the inner layer(s) may contain an in-situ polymerized conductive polymer.
  • the in- situ polymerized polymers may constitute about 50 wt.% or more, in some embodiments about 70 wt.% or more, and in some embodiments, about 90 wt.% or more (e.g., 100 wt.%) of the inner layer(s).
  • the solid electrolyte may also contain one or more optional "outer" conductive polymer layers that overly the inner layer(s) and are formed from a different material.
  • the outer layer(s) may contain extrinsically conductive polymer particles.
  • the outer layer(s) are formed primarily from such extrinsically conductive polymer particles in that they constitute about 50 wt.% or more, in some embodiments about 70 wt.% or more, and in some embodiments, about 90 wt.% or more (e.g., 100 wt.%) of a respective outer layer.
  • One or multiple outer layers may be employed.
  • the solid electrolyte may contain from 2 to 30, in some embodiments from 4 to 20, and in some embodiments, from about 5 to 15 outer layers, each of which may optionally be formed from a dispersion of the extrinsically conductive polymer particles.
  • An external polymer coating may also overly the solid electrolyte.
  • the external polymer coating generally contains one or more layers formed from pre- polymerized conductive polymer particles such as described above (e.g., dispersion of extrinsically conductive polymer particles).
  • the external coating may be able to further penetrate into the edge region of the capacitor body to increase the adhesion to the dielectric and result in a more mechanically robust part, which may reduce equivalent series resistance and leakage current. Because it is generally intended to improve the degree of edge coverage rather to impregnate the interior of the anode body, the particles used in the external coating typically have a larger size than those employed in the solid electrolyte.
  • the ratio of the average size of the particles employed in the external polymer coating to the average size of the particles employed in any dispersion of the solid electrolyte is typically from about 1 .5 to about 30, in some embodiments from about 2 to about 20, and in some embodiments, from about 5 to about 15.
  • the particles employed in the dispersion of the external coating may have an average size of from about 80 to about 500 nanometers, in some embodiments from about 90 to about 250 nanometers, and in some embodiments, from about 100 to about 200 nanometers.
  • a crosslinking agent may also be employed in the external polymer coating to enhance the degree of adhesion to the solid electrolyte.
  • the crosslinking agent is applied prior to application of the dispersion used in the external coating.
  • Suitable crosslinking agents are described, for instance, in U.S. Patent Publication No. 2007/0064376 to Merker, et al. and include, for instance, amines (e.g., diamines, triamines, oligomer amines, polyamines, etc.); polyvalent metal cations, such as salts or compounds of Mg, Al, Ca, Fe, Cr, Mn, Ba, Ti, Co, Ni, Cu, Ru, Ce or Zn, phosphonium compounds, sulfonium compounds, etc.
  • amines e.g., diamines, triamines, oligomer amines, polyamines, etc.
  • polyvalent metal cations such as salts or compounds of Mg, Al, Ca, Fe, Cr, Mn, Ba, Ti, Co, Ni, Cu, Ru, Ce or Zn, phosphonium compounds, sulfonium compounds, etc.
  • Particularly suitable examples include, for instance, 1 ,4-diaminocyclohexane, 1 ,4-bis(amino-methyl)cyclohexane, ethylenediamine, 1 ,6- hexanediamine, 1 ,7-heptanediamine, 1 ,8-octanediamine, 1 ,9-nonanediamine, 1 , 10-decanediamine, 1 , 12-dodecanediamine, N,N-dimethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1 ,4-butanediamine, etc., as well as mixtures thereof.
  • the crosslinking agent is typically applied from a solution or dispersion whose pH is from 1 to 10, in some embodiments from 2 to 7, in some
  • the crosslinking agent may be applied to the capacitor body by any known process, such as spin-coating, impregnation, casting, dropwise application, spray application, vapor deposition, sputtering, sublimation, knife-coating, painting or printing, for example inkjet, screen or pad printing. Once applied, the crosslinking agent may be dried prior to application of the polymer dispersion. This process may then be repeated until the desired thickness is achieved.
  • the total thickness of the entire external polymer coating, including the crosslinking agent and dispersion layers may range from about 1 to about 50 pm, in some embodiments from about 2 to about 40 pm, and in some embodiments, from about 5 to about 20 pm.
  • the capacitor element may also employ a cathode coating that overlies the solid electrolyte and other optional layers (e.g., external polymer coating).
  • the cathode coating may contain a metal particle layer includes a plurality of conductive metal particles dispersed within a resinous polymer matrix.
  • the particles typically constitute from about 50 wt.% to about 99 wt.%, in some embodiments from about 60 wt.% to about 98 wt.%, and in some embodiments, from about 70 wt.% to about 95 wt.% of the layer, while the resinous polymer matrix typically constitutes from about 1 wt.% to about 50 wt.%, in some
  • the conductive metal particles may be formed from a variety of different metals, such as copper, nickel, silver, nickel, zinc, tin, lead, copper, aluminum, molybdenum, titanium, iron, zirconium, magnesium, etc., as well as alloys thereof.
  • Silver is a particularly suitable conductive metal for use in the layer.
  • the metal particles often have a relatively small size, such as an average size of from about 0.01 to about 50 micrometers, in some embodiments from about 0.1 to about 40 micrometers, and in some embodiments, from about 1 to about 30 micrometers. Typically, only one metal particle layer is employed, although it should be understood that multiple layers may be employed if so desired.
  • the total thickness of such layer(s) is typically within the range of from about 1 pm to about 500 pm, in some embodiments from about 5 pm to about 200 pm, and in some embodiments, from about 10 pm to about 100 pm.
  • the resinous polymer matrix typically includes a polymer, which may be thermoplastic or thermosetting in nature.
  • the polymer is selected so that it can act as a barrier to electromigration of silver ions, and also so that it contains a relatively small amount of polar groups to minimize the degree of water adsorption in the cathode coating.
  • vinyl acetal polymers are particularly suitable for this purpose, such as polyvinyl butyral, polyvinyl formal, etc.
  • Polyvinyl butyral for instance, may be formed by reacting polyvinyl alcohol with an aldehyde (e.g., butyraldehyde).
  • polyvinyl butyral will generally have a residual hydroxyl content. By minimizing this content, however, the polymer can possess a lesser degree of strong polar groups, which would otherwise result in a high degree of moisture adsorption and result in silver ion migration.
  • the residual hydroxyl content in polyvinyl acetal may be about 35 mol.% or less, in some embodiments about 30 mol.% or less, and in some embodiments, from about 10 mol.% to about 25 mol.%.
  • BH- S polyvinyl butyral
  • a conductive paste is typically applied to the capacitor that overlies the solid electrolyte.
  • One or more organic solvents are generally employed in the paste.
  • a variety of different organic solvents may generally be employed, such as glycols (e.g., propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, polyethylene glycols, ethoxydiglycol, and dipropyleneglycol); glycol ethers (e.g., methyl glycol ether, ethyl glycol ether, and isopropyl glycol ether); ethers (e.g., diethyl ether and tetrahydrofuran); alcohols (e.g., benzyl alcohol, methanol, ethanol, n-propanol, iso-propanol, and butanol); triglycerides; ketones (e.g., acetone, methyl ethyl ketone, and methyl is
  • the metal particles constitute from about 10 wt.% to about 60 wt.%, in some
  • the resinous polymer matrix constitutes from about 0.1 wt.% to about 20 wt.%, in some embodiments from about 0.2 wt.% to about 10 wt.%, and in some embodiments, from about 0.5 wt.% to about 8 wt.% of the paste.
  • the paste may have a relatively low viscosity, allowing it to be readily handled and applied to a capacitor element.
  • the viscosity may, for instance, range from about 50 to about 3,000 centipoise, in some embodiments from about 100 to about 2,000 centipoise, and in some embodiments, from about 200 to about 1 ,000 centipoise, such as measured with a Brookfield DV-1 viscometer (cone and plate) operating at a speed of 10 rpm and a temperature of 25°C.
  • thickeners or other viscosity modifiers may be employed in the paste to increase or decrease viscosity.
  • the thickness of the applied paste may also be relatively thin and still achieve the desired properties.
  • the thickness of the paste may be from about 0.01 to about 50 micrometers, in some
  • the metal paste may be optionally dried to remove certain components, such as the organic solvents. For instance, drying may occur at a temperature of from about 20°C to about 150°C, in some embodiments from about 50°C to about 140°C, and in some embodiments, from about 80°C to about 130°C.
  • the capacitor may also contain other layers as is known in the art.
  • a carbon layer e.g., graphite
  • a pre-coat layer may be employed in certain embodiments that overlies the dielectric and includes an organometallic compound, such as described in more detail below.
  • the capacitor assembly may be provided with terminations.
  • the capacitor assembly may contain an anode termination to which an anode lead of the capacitor element is electrically connected and a cathode termination to which the cathode of the capacitor element is electrically connected.
  • Any conductive material may be employed to form the terminations, such as a conductive metal (e.g., copper, nickel, silver, nickel, zinc, tin, palladium, lead, copper, aluminum, molybdenum, titanium, iron, zirconium, magnesium, and alloys thereof).
  • Particularly suitable conductive metals include, for instance, copper, copper alloys (e.g., copper-zirconium, copper- magnesium, copper-zinc, or copper-iron), nickel, and nickel alloys (e.g., nickel- iron).
  • the thickness of the terminations is generally selected to minimize the thickness of the capacitor. For instance, the thickness of the terminations may range from about 0.05 to about 1 millimeter, in some embodiments from about 0.05 to about 0.5 millimeters, and from about 0.07 to about 0.2 millimeters.
  • One exemplary conductive material is a copper-iron alloy metal plate available from Wieland (Germany). If desired, the surface of the terminations may be
  • both surfaces of the terminations are plated with nickel and silver flashes, respectively, while the mounting surface is also plated with a tin solder layer.
  • At least a portion of the anode termination contains a first coating and at least a portion of the cathode termination contains a second coating.
  • the first and coating may be formed from the same or different materials.
  • both the first and second coatings contain an organometallic compound, which may have the following general formula:
  • M is an organometallic atom, such as silicon, titanium, and so forth;
  • R-i , R 2 , and R 3 are independently an alkyl (e.g., methyl, ethyl, propyl, etc.) or a hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, etc.), wherein at least one of R-i, R 2 , and R 3 is a hydroxyalkyl;
  • n is an integer from 0 to 8, in some embodiments from 1 to 6, and in some embodiments, from 2 to 4 (e.g., 3); and
  • X is an organic or inorganic functional group, such as glycidyl, glycidyloxy, mercapto, amino, vinyl, etc.
  • R-i, R 2 , and R 3 may a hydroxyalkyl (e.g., OCH 3 ).
  • Ri may be an alkyl (e.g., CH 3 ) and R 2 and R 3 may a hydroxyalkyl (e.g., OCH 3 ).
  • M may be silicon so that the
  • organometallic compound is an organosilane compound, such as an alkoxysilane.
  • Suitable alkoxysilanes may include, for instance, 3-aminopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- aminopropylmethyldiethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3- mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyl- tripropoxysilane, glycidoxymethyltributoxysilane, ⁇ -glycidoxyethyltrime
  • first and second coatings are applied to their respective terminations may vary as desired. In one particular
  • an organometallic compound is dissolved in an organic solvent to form a solution, which can then be coated onto a termination.
  • Suitable coating techniques may include, for instance, screen-printing, dipping, electrophoretic coating, spraying, etc.
  • the organic solvent may vary, but is typically an alcohol, such as methanol, ethanol, etc.
  • Organometallic compounds may constitute from about 0.1 wt.% to about 10 wt.%, in some embodiments from about 0.2 wt.% to about 8 wt.%, and in some embodiments, from about 0.5 wt.% to about 5 wt.% of the solution.
  • Solvents may likewise constitute from about 90 wt.% to about 99.9 wt.%, in some embodiments from about 92 wt.% to about 99.8 wt.%, and in some embodiments, from about 95 wt.% to about 99.5 wt.% of the solution.
  • the particular location of a coating on a given termination may also vary as desired.
  • it is desired that at least one surface of a termination (e.g. , anode termination and/or cathode termination) that is in contact with the casing material contains a coating.
  • the upper surface, lower surface, and/or edges of a termination may contain a coating.
  • the coating may cover the entire surface(s) of a termination, or it may be applied in a pattern.
  • each surface of the anode termination contains the first coating and each surface of the cathode termination contains the second coating.
  • the coatings may then be cured to ensure the desired degree of adhesion to the terminations. Curing may occur before, after, and/or during the process in which the casing material is applied. Typically, the curing process is performed at a relatively high temperature, such as a
  • temperature of from about 50°C to about 250°C, in some embodiments from about 80°C to about 200°C, and in some embodiments, from about 100°C to about 150°C.
  • a capacitor assembly 30 is shown as including an anode termination 62 and a cathode termination 72 in electrical connection with a capacitor element 33.
  • the cathode termination 72 in the illustrated embodiment is in electrical contact with the lower surface 39 via a conductive adhesive. More specifically, the cathode termination 72 contains a first component 73 that is in electrical contact and generally parallel with the lower surface 39 of the capacitor element 33.
  • the cathode termination 72 may also contain a second component 74 that is substantially perpendicular to the first component 73 and in electrical contract with a rear surface 38 of the capacitor element 33.
  • the anode termination 62 likewise contains a first component 63 positioned substantially perpendicular to a second component 64.
  • the first component 63 is in electrical contact and generally parallel with the lower surface 39 of the capacitor element 33.
  • the second component 64 contains a region 51 that carries an anode lead 16.
  • at least a portion of the anode termination 62 e.g., first component 63 and/or second component 64
  • contains the first coating not shown
  • at least a portion of the cathode termination 72 e.g., first component 73 and/or second component 73
  • the second component 64 of the anode termination 62 is initially bent upward to the position shown in Fig. 1 . Thereafter, the capacitor element 33 is positioned on the cathode termination 72 so that its lower surface 39 contacts the adhesive and the anode lead 16 is received by the region 51.
  • an insulating material (not shown), such as a plastic pad or tape, may be positioned between the lower surface 39 of the capacitor element 33 and the first component 63 of the anode termination 62 to electrically isolate the anode and cathode terminations.
  • the anode lead 16 is then electrically connected to the region 51 using any technique known in the art, such as mechanical welding, laser welding, conductive adhesives, etc.
  • the anode lead 16 may be welded to the anode termination 62 using a laser.
  • Lasers generally contain resonators that include a laser medium capable of releasing photons by stimulated emission and an energy source that excites the elements of the laser medium.
  • One type of suitable laser is one in which the laser medium consist of an aluminum and yttrium garnet (YAG), doped with neodymium (Nd).
  • the excited particles are neodymium ions Nd 3+ .
  • the energy source may provide continuous energy to the laser medium to emit a continuous laser beam or energy discharges to emit a pulsed laser beam.
  • the conductive adhesive may then be cured.
  • a heat press may be used to apply heat and pressure to ensure that the electrolytic capacitor element 33 is adequately adhered to the cathode termination 72 by the adhesive.
  • the capacitor element is generally encapsulated with a casing material so that at least a portion of the anode and cathode terminations are exposed for mounting onto a circuit board.
  • the capacitor element 33 may be encapsulated within a casing material 28 so that a portion of the anode termination 62 and a portion of the cathode termination 72 are exposed.
  • the casing material may contain an epoxy composition that contains one or more inorganic oxide fillers and a resinous material that includes one more epoxy resins optionally crosslinked with a co- reactant (hardener).
  • a co- reactant hardener
  • the content of the inorganic oxide fillers is maintained at a high level, such as about 75 wt.% or more, in some embodiments about 76 wt.% or more, and in some embodiments, from about 77 wt.% to about 90 wt.% of the composition.
  • the nature of the inorganic oxide fillers may vary, such as silica, alumina, zirconia, magnesium oxides, iron oxides (e.g., iron hydroxide oxide yellow), titanium oxides (e.g., titanium dioxide), zinc oxides (e.g., boron zinc hydroxide oxide), copper oxides, zeolites, silicates, clays (e.g., smectite clay), etc., as well as composites (e.g., alumina-coated silica particles) and mixtures thereof.
  • magnesium oxides such as silica, alumina, zirconia, magnesium oxides, iron oxides (e.g., iron hydroxide oxide yellow), titanium oxides (e.g., titanium dioxide), zinc oxides (e.g., boron zinc hydroxide oxide), copper oxides, zeolites, silicates, clays (e.g., smectite clay), etc., as well as composites (e.g., a
  • inorganic oxide fillers typically in the form of vitreous silica, which is believed to further improve the moisture resistance of the casing material due to its high purity and relatively simple chemical form.
  • Vitreous silica may, for instance, constitute about 30 wt.% or more, in some embodiments from about 35 wt.% to about 90 wt.%, and in some embodiments, from about 40 wt.% to about 80 wt.% of the total weight of fillers employed in the composition, as well as from about 20 wt.% to about 70 wt.%, in some embodiments from about 25 wt.% to about 65 wt.%, and in some embodiments, from about 30 wt.% to about 60 wt.% of the entire composition.
  • other forms of silica may also be employed in combination with the vitreous silica, such as quartz, fumed silica, cristabolite, etc.
  • the resinous material typically constitutes from about 0.5 wt.% to about 25 wt.%, in some embodiments from about 1 wt.% to about 24 wt.%, and in some embodiments, from about 10 wt.% to about 23 wt.% of the composition.
  • any of a variety of different types of epoxy resins may be employed in the present invention.
  • suitable epoxy resins include, for instance, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, brominated epoxy resins and biphenyl type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, cresol novolac type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, cyclopentadiene type epoxy resins, heterocyclic epoxy resins, etc.
  • EPN epoxy phenol novolac
  • resins which are glycidyl ethers of phenolic novolac resins.
  • EPN resins can be prepared, for example, by reaction of phenols with an excess of formaldehyde in the presence of an acidic catalyst to produce the phenolic novolac resin.
  • Novolac epoxy resins are then prepared by reacting the phenolic novolac resin with epichlorihydrin in the presence of sodium hydroxide.
  • the novolac-type epoxy resins include a phenol-novolac epoxy resin, cresol-novolac epoxy resin, naphthol-novolac epoxy resin, naphthol- phenol co-condensation novolac epoxy resin, naphthol-cresol co-condensation novolac epoxy resin, brominated phenol-novolac epoxy resin, etc.
  • the resulting phenolic novolac epoxy resins typically have more than two oxirane groups and can be used to produce cured coating compositions with a high crosslinking density, which can be particularly suitable for enhancing moisture resistance.
  • One such phenolic novolac epoxy resin is poly[(phenyl glycidyl ether)-co-formaldehyde].
  • Other suitable resins are
  • ARALDITE e.g., GY289, EPN 1 183, EP 1 179, EPN 1 139, and EPN 1 138
  • the epoxy resin may optionally be crosslinked with a co- reactant (hardener) to further improve the mechanical properties of the epoxy resin.
  • a co- reactant hardener
  • composition and also enhance its overall moisture resistance as noted above.
  • co-reactants may include, for instance, polyamides,
  • amidoamines e.g., aromatic amidoamines such as aminobenzamides
  • aminobenzanilides, and aminobenzenesulfonamides include aromatic diamines (e.g., diaminodiphenylmethane, diaminodiphenylsulfone, etc.), aminobenzoates (e.g., trimethylene glycol di-p-aminobenzoate and neopentyl glycol di-p-amino- benzoate), aliphatic amines (e.g., triethylenetetramine, isophoronediamine), cycloaliphatic amines (e.g., isophorone diamine), imidazole derivatives, guanidines (e.g., tetramethylguanidine), carboxylic acid anhydrides (e.g.,
  • Phenolic-novolac resins may be particularly suitable for use in the present invention.
  • additives may also be employed in the epoxy composition used to form the casing, such as photoinitiators, viscosity modifiers, suspension aiding agents, pigments, stress reducing agents, coupling agents (e.g., silane coupling agents), stabilizers, etc.
  • photoinitiators e.g., photoinitiators
  • viscosity modifiers e.g., viscosity modifiers
  • suspension aiding agents e.g., suspension aiding agents
  • pigments e.g., pigments
  • stress reducing agents e.g., silane coupling agents
  • coupling agents e.g., silane coupling agents
  • stabilizers e.g., silane coupling agents
  • the particular manner in which the casing material is applied to the capacitor body may vary as desired.
  • the capacitor element is placed in a mold and the casing material is applied to the capacitor element so that it occupies the spaces defined by the mold and leaves exposed at least a portion of the anode and cathode terminations.
  • the casing material may be initially provided in the form of a single or multiple compositions.
  • a first composition may contain the epoxy resin and the second composition may contain the co-reactant.
  • the casing material may be heated or allowed to stand at ambient temperatures so that the epoxy resin is allowed to crosslink with the co-reactant, which thereby causes the epoxy composition to cure and harden into the desired shape of the case.
  • the composition may be heated to a temperature of from about 15°C to about 150°C, in some embodiments from about 20°C to about 120°C, and in some embodiments, from about 25°C to about 100°C.
  • a moisture barrier layer may also be employed that coats all or a portion of the casing material.
  • the moisture barrier layer is generally formed from a hydrophobic elastomer, such as silicones, fluoropolymers, etc. Silicone elastomers are particularly suitable for use in the moisture barrier layer of the present invention. Such elastomers are typically derived from polyorganosiloxanes, such as those having the following general formula:
  • x is an integer greater than 1 ;
  • Ri , R2, R3, R4, R5, R6, R7, and R 8 are independently monovalent groups typically containing from 1 to about 20 carbon atoms, such as alkyl groups (e.g., methyl, ethyl, propyl, pentyl, octyl, undecyl, octadecyl, etc.); alkoxy groups (e.g., methoxy, ethoxy, propoxy, etc.); carboxyalkyl groups (e.g., acetyl); cycloalkyl groups (e.g., cyclohexyl); alkenyl groups (e.g., vinyl, allyl, butenyl, hexenyl, etc.); aryl groups (e.g., phenyl, tolyl, xylyl, benzyl, 2-phenylethyl, etc.); and halogenated hydrocarbon groups (e.g., 3,3,3-trifluoropropyl
  • polyorganosiloxanes may include, for instance, polydimethylsiloxane ("PDMS"), polymethylhydrogensiloxane, dimethyidiphenylpolysiloxane, dimethyl/methylphenylpolysiloxane, polymethylphenylsiloxane, methylphenyl/dimethylsiloxane, vinyldimethyl terminated polydimethylsiloxane, vinylmethyl/dimethylpolysiloxane, vinyldimethyl terminated vinylmethyl/dimethylpolysiloxane, divinylmethyl terminated
  • PDMS polydimethylsiloxane
  • polymethylhydrogensiloxane dimethyidiphenylpolysiloxane
  • dimethyl/methylphenylpolysiloxane polymethylphenylsiloxane
  • polymethylphenyl/dimethylsiloxane vinyldimethyl terminated polydimethylsiloxane
  • polydimethylsiloxane vinylphenylmethyl terminated polydimethylsiloxane, dimethylhydro terminated polydimethylsiloxane, methylhydro/dimethylpolysiloxane, methylhydro terminated methyloctylpolysiloxane, methylhydro/phenylmethyl polysiloxane, fluoro-modified polysiloxane, etc.
  • the polyorganosiloxane may be crosslinked using any of a variety of known
  • Crosslinking agents may be employed, such as alkoxy silanes having the formula Si-OR, wherein R is H, alkyl (e.g., methyl), alkenyl, carboxyalkyl (e.g., acetyl), and so forth.
  • the material used to form the moisture barrier layer has a relatively low modulus and a certain degree of flexibility, which can help absorb some of the thermal stresses caused by expansion of the casing and also allow it to be subjected to compressive forces.
  • the flexibility of the material may be characterized by a corresponding low modulus of elasticity ("Young's modulus”), such as about 5,000 kilopascals (“kPa”) or less, in some embodiments from about 1 to about 2,000 kPa, and in some embodiments, from about 2 to about 500 kPa, measured at a temperature of about 25°C.
  • Young's modulus such as about 5,000 kilopascals (“kPa”) or less, in some embodiments from about 1 to about 2,000 kPa, and in some embodiments, from about 2 to about 500 kPa, measured at a temperature of about 25°C.
  • the material also typically possesses a certain degree of strength that allows it to retain its shape even when subjected to compressive forces.
  • the material may possess a tensile strength of from about 1 to about 5,000 kPa, in some embodiments from about 10 to about 2,000 kPa, and in some embodiments, from about 50 to about 1 ,000 kPa, measured at a temperature of about 25°C.
  • the hydrophobic elastomer can even further enhance the ability of the capacitor to function under extreme conditions.
  • a non- conductive filler may be employed in the moisture barrier layer.
  • such additives typically constitute from about 0.5 wt.% to about 30 wt.%, in some embodiments from about 1 wt.% to about 25 wt.%, and in some embodiments, from about 2 wt.% to about 20 wt.% of the moisture barrier layer.
  • the silicone elastomer may constitute from about 70 wt.% to about 99.5 wt.%, in some embodiments from about 75 wt.% to about 99 wt.%, and in some embodiments, from about 80 wt.% to about 98 wt.% of the moisture barrier layer.
  • silica includes, for instance, silica. While most forms of silica contain a relatively hydrophilic surface due to the presence of silanol groups (Si- OH), the silica may optionally be surface treated so that its surface contains (CH 3 ) n -Si- groups, wherein n is an integer of 1 to 3, which further enhances the hydrophobicity of the moisture barrier layer.
  • the surface treatment agent may, for example, be an organosilicon compound monomer having a hydrolyzable group or a partial hydrolyzate thereof. Examples of such compounds may include organosilazanes, silane coupling agents such as described above, etc.
  • the resulting capacitor assembly can exhibit a variety of beneficial properties.
  • the dissipation factor of the capacitor assembly may be maintained at relatively low levels.
  • the dissipation factor generally refers to losses that occur in the capacitor and is usually
  • the dissipation factor of the capacitor of the present invention is typically from about 1 % to about 25%, in some embodiments from about 3% to about 10%, and in some embodiments, from about 5% to about 15%, as determined at a frequency of 120 Hz.
  • the capacitor assembly may also be able to be employed in high voltage applications, such as at rated voltages of about 35 volts or more, in some embodiments about 50 volts or more, and in some embodiments, from about 60 volts to about 200 volts.
  • the capacitor assembly may, for example, exhibit a relatively high "breakdown voltage" (voltage at which the capacitor fails), such as about 2 volts or more, in some embodiments about 5 volts or more, in some embodiments about 10 volts or more, and in some embodiments, from about 10 to about 100 volts.
  • the capacitor assembly may also be able to withstand relatively high surge currents, which is also common in high voltage applications.
  • the peak surge current may be, for example, about 100 Amps or more, in some embodiments about 200 Amps or more, and in some embodiments, and in some embodiments, from about 300 Amps to about 800 Amps.
  • Equivalence series resistance may be measured using a Keithley 3330 Precision LCZ meter with Kelvin Leads 2.2 volt DC bias and a 0.5 volt peak to peak sinusoidal signal.
  • the operating frequency may 100 kHz and the
  • temperature may be 23°C + 2°C.
  • the dissipation factor may be measured using a Keithley 3330 Precision LCZ meter with Kelvin Leads with 2.2 volt DC bias and a 0.5 volt peak to peak sinusoidal signal.
  • the operating frequency may be 120 Hz and the temperature may be 23°C + 2°C.
  • the capacitance may be measured using a Keithley 3330 Precision LCZ meter with Kelvin Leads with 2.2 volt DC bias and a 0.5 volt peak to peak sinusoidal signal.
  • the operating frequency may be 120 Hz and the temperature may be 23°C + 2°C.
  • Leakage current may be measured using a leakage test meter at a temperature of 23°C + 2°C and at the rated voltage (e.g., 16 volts) after a minimum of 60 seconds (e.g., 180 seconds, 300 seconds).
  • a leakage test meter at a temperature of 23°C + 2°C and at the rated voltage (e.g., 16 volts) after a minimum of 60 seconds (e.g., 180 seconds, 300 seconds).
  • Moisture sensitivity level testing may be conducted (50 parts) after exposure to a temperature of 30°C and 60% relative humidity for a period of 24 hours, 48 hours. Electrical parameters and external cracks via using optical microscope can be recorded after the reflow at recovered samples and then compared.
  • 70,000 FV/g tantalum powder was used to form anode samples.
  • Each anode sample was embedded with a tantalum wire, sintered at 1410°C, and pressed to a density of 5.1 g/cm 3 .
  • the resulting pellets had a size of 5.60 x 3.65 x 0.90 mm.
  • the pellets were anodized to 71.0 volts in water/phosphoric acid electrolyte with a conductivity of 8.6 mS at a temperature of 85°C to form the dielectric layer.
  • the pellets were anodized again to 150 volts in a water/boric acid/disodium tetraborate with a conductivity of 2.0 mS at a temperature of 30°C for 25 seconds to form a thicker oxide layer built up on the outside.
  • the conductive polymer coating was formed by dipping the anodes into a dispersed poly(3,4-ethylenedioxythiophene) having a solids content 1.1 % and viscosity 20 mPa.s (CleviosTM K, Heraeus) directly without the pre-coat layer. Upon coating, the parts were dried at 125°C for 20 minutes. This process was repeated 10 times. Thereafter, the parts were dipped into a dispersed poly(3,4- ethylenedioxythiophene) having a solids content 2.0% and viscosity 20 mPa.s (CleviosTM K, Heraeus). Upon coating, the parts were dried at 125°C for 20 minutes. This process was repeated 3 times.
  • the parts were dipped into a dispersed poly(3,4-ethylenedioxythiophene) having a solids content of 2% and viscosity 160 mPa.s (CleviosTM K, Heraeus). Upon coating, the parts were dried at 125°C for 20 minutes. This process was repeated 8 times. The parts were then dipped into a graphite dispersion and dried. Finally, the parts were dipped into a silver dispersion and dried. Multiple parts (3000) of 47 ⁇ /35 ⁇ capacitors were made in this manner and encapsulated in a silica resin.
  • Capacitors were formed in the manner described in Example 1 , except that three (3) layers of an organometallic solution were applied to the anode and cathode portions of the leadframe before encapsulation with the silica resin. More particularly, the solution contained (3-glycidyloxypropyl)trimethoxysilane in ethanol (1.0%). Multiple parts (3000) of 47 ⁇ /35 ⁇ capacitors were formed.
  • Table 1 The median results of electrical parameters within moisture sensitivity level testing are set forth below in Table 1.
  • the external cracks within moisture sensitivity level testing from the top and the bottom side of capacitors are set forth below in Table 2.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un ensemble condensateur qui est capable de fonctionner correctement dans des conditions d'humidité élevée (par exemple, 60 % d'humidité relative). L'ensemble condensateur comporte un élément condensateur à électrolyte solide qui comprend un corps d'anode poreux fritté, un diélectrique qui recouvre le corps d'anode, et un électrolyte solide qui recouvre le diélectrique. Une terminaison d'anode est en connexion électrique avec le corps d'anode et une terminaison de cathode est en connexion électrique avec l'électrolyte solide. Un premier revêtement est disposé sur au moins une partie de la terminaison d'anode qui contient un composé organométallique et un second revêtement est disposé sur au moins une partie de la terminaison de cathode qui contient un composé organométallique. En outre, un matériau de boîtier encapsule l'élément de condensateur et laisse découverte une surface de montage de la terminaison d'anode et de la terminaison de cathode.
EP18763444.9A 2017-03-06 2018-03-06 Ensemble condensateur à électrolyte solide Pending EP3593367A4 (fr)

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US10622160B2 (en) 2020-04-14
EP3593367A4 (fr) 2021-01-20
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CN115881437A (zh) 2023-03-31
US20180254151A1 (en) 2018-09-06

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